Multi-layer structures prepared by layer-by-layer assembly

ABSTRACT

A protective layer can be deposited on a surface of an porous polymer separator placing on a Li-metal electrode to protect against adverse electrochemical activity in a battery. The protective layer can be a multilayered structure including graphene oxide.

CLAIM OF PRIORITY

This application is a divisional application of U.S. application Ser.No. 14/143,803, filed on Dec. 30, 2013, which claims the benefit ofprior U.S. Provisional Application No. 61/748,089, filed on Jan. 1,2013, each of which is incorporated by reference in its entirety.

TECHNICAL FIELD

The invention relates to multi-layered structures and methods ofproducing multi-layer structures.

BACKGROUND

Energy consumption and global climate change suggest looking for analternative energy conversion/storage system. Lithium-air batteries haveshown promising electrochemical performance. However, for practicalapplications, lithium-air batteries face some challenges, such asdevelopment of electrochemically stable electrolyte, optimized structureof air electrode, and suppression of dendritic growth on lithium anode.

SUMMARY

In general, A protective layer can be deposited on a surface of anporous polymer separator placing on a Li-metal electrode to protectagainst adverse electrochemical activity in a battery. The protectivelayer can be a multilayered structure including graphene oxide.

In one aspect, a method of preparing a multi-layer structure on asubstrate includes forming a pair of bilayers on a surface of thesubstrate, the first bilayer including a first material and a secondmaterial wherein the first material and the second material areoppositely charged materials or materials otherwise having affinity foreach other, the second bilayer including a third material and a fourthmaterial wherein the third material and the fourth material areoppositely charged materials or materials otherwise having affinity foreach other, and the pair of bilayers including ion-conductive polymerand a barrier layer.

In certain embodiments, preparing the multi-layer structure can includecontacting the membrane with a first solution containing the firstmaterial, contacting the membrane with a second solution containing thesecond material, contacting the membrane with a third solutioncontaining the third material, and contacting the membrane with a fourthsolution containing the fourth material. The first material and thethird material can be the same or different. The second material and thefourth material can be the same or different.

In certain embodiments, the substrate can include a membrane, such as,for example, polypropylene or can be glass. The substrate can be plasmatreated.

In certain embodiments, the first solution, the second solution, thethird solution, and the fourth solution can be adjusted for hydrogenbonding between materials in the bilayers.

In certain embodiments, each solution, independently and optionally, caninclude a lithium salt, such as lithium bis(oxalate)borate, polyethyleneoxide, graphene oxide, or polyacrylic acid.

In certain embodiments, the first material can be polyethylene oxide,the second material can be graphene oxide, the third material can bepolyethylene oxide, and the fourth material can be polyacrylic acid. Thematerials can form a pair of bilayers on a polypropylene membrane.

In another aspect, a multi-layer structure can include a tetralayer,wherein the tetralayer can include an ion-conductive polymer and abarrier layer.

In certain embodiments, the tetralayer can be on a substrate and caninclude graphene oxide, polyethylene oxide, or polyacrylic acid. Thetetralayer can include a first polyethylene oxide layer, a grapheneoxide layer adjacent to the first polyethylene oxide layer, a secondpolyethylene oxide layer adjacent to the graphene oxide layer andopposite the first polyethylene oxide layer, and a polyacrylic acidlayer adjacent to the second polyethylene oxide layer. The surface ofthe tetralayer can be more hydrophilic than a surface of the substrate.The thickness of the structure can increase as the number of tetralayersincreases. The thickness of the tetralayer can change the ionicconductivities of the structure. The electrolyte permeability in thelayer can be repressed with increasing thickness of the tetralayer, forexample, graphene oxide can lower the permeability.

In another aspect, a battery device can include an electrode protectivestructure, wherein the electrode protective structure can includegraphene oxide.

In certain embodiments, the battery can be a lithium battery, such as alithium-air battery. The electrode protective structure contacts asurface of an anode. The electrode protective structure can include anion-conductive polymer, and, optionally, a barrier layer. The electrodeprotective structure can include a first polyethylene oxide layer, agraphene oxide layer adjacent to the first polyethylene oxide layer, asecond polyethylene oxide layer adjacent to the graphene oxide layer andopposite the first polyethylene oxide layer, and a polyacrylic acidlayer adjacent to the second polyethylene oxide layer. The electrodeprotective layers suppress dendritic growth on an electrode, such as alithium anode.

Other aspects, embodiments, and features will be apparent from thefollowing description, the drawings, and the claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic drawing depicting a multilayer structure.

FIG. 2 is a schematic drawing depicting a battery.

FIG. 3(a) is a C1s X-ray photoelectron spectroscopy (XPS) scan and FIG.3(b) is an atomic force microscopy (AFM) image of graphene oxide (GO).

FIG. 4(a) is a schematic illustration of layer-by-layer (LbL) assemblyon polypropylene (PP) membrane; FIG. 4(b) is a scanning electronmicroscope (SEM) top-down image of pristine porous PP membrane; FIG.4(c) is an SEM top-down image of polymer top layer after LbL-assembly onpristine membrane; FIG. 4(d) is an AFM image of graphene oxide top layerduring LbL-assembly; and FIG. 4(e) is an SEM cross sectional image of 12tetralayers of LbL-assembly on a porous membrane.

FIG. 5(a) is an SEM top-view image of polypropylene (PP) membrane afterO₂ plasma treatment for 30 seconds; FIG. 5(b) is water contact anglemeasurement of LbL-modified side; and FIG. 5(c) is water contact anglemeasurement of bare PP side of LbL-modified membrane.

FIG. 6(a) shows the thickness change of LbL layers versus the number oftetralayers; FIG. 6(b) shows ionic conductivities of pristine membraneand LbL-assembled membrane with GO; FIG. 6(c) shows electrolytepermeabilities of whole LbL-assembled membranes (PP membrane+LbL layers)with and without GO incorporation; and FIG. 6(d) shows the calculatedintrinsic permeabilities of LbL layers without support membrane. Reddots/bars are for (PEO/GO/PEO/P AA)_(n) and black dots/bars are for(PEO/P AA)_(2n). n means the number of tetralayers.

FIGS. 7(a) and 7(b) show comparisons of thickness and ionicconductivities of LbL modified membranes under three circumstances: LbLwith GO and without LiBOB in polymer solution (black), LbL with GO andLiBOB in polymer solution (red), and LbL without GO and with LiBOB inpolymer solution (blue).

FIG. 8(a) shows chronoamperogram of 12-tetralayer LbL-assembledmembranes with and without incorporation of GO at a constant potentialof 10 mV; FIG. 8(b) shows a comparison of impedance spectra before andafter tests for Li transfer number; and FIG. 8(c) shows the effect ofthe LbL layer thickness and presence of GO on Li transfer number of LbLassembled membranes.

FIG. 9(a) shows chronopotentiogram of pristine and LbL-assembledmembranes bearing GO or not at a constant current density of 0.2 mA/cm²;FIG. 9(b) shows cyclability test of LbL-assembled membrane with orwithout GO at constant current density varying its polarity every 4hours.

FIG. 10 shows cyclability test of pristine membrane at 0.2 mA/cm² ofconstant current density varying its polarity every 4 hours.

FIG. 11 is a table that shows a comparison of short-circuit time of testcells, thickness and roughness for pristine and LbL-assembled membraneswith and without GO.

DETAILED DESCRIPTION

Layer-by-layer (LbL) assembly is a method for fabricating thin films bysequential adsorption of two or more materials with complementaryfunctional groups or materials otherwise having affinity for each other.Typically, positively and negatively charged materials are used. LbLassembly can also be accomplished by hydrogen bonding, covalent bonding,as well as other specific interactions. LbL technique can be used todeposit a variety of materials including polymers, metals, ceramics,nanomaterials, biological molecules, micelles, small molecules, andother materials that can become charged or having affinity whendissolved in a solvent.

LbL multilayer films can be prepared in many different ways includingdip-coating, spray-coating, and spin-coating. In dip-coating, asubstrate is immersed in a solution containing a first coating material.The substrate can remain in the solution for a while before being pulledup. Excess liquid on the surface of the substrate can be washed,drained, or evaporated. The substrate is then immersed in a solutioncontaining a second coating material. A spray LbL method uses alternatespray, instead of alternate dipping, of solutions or suspensions. Spincoating is a procedure where an excess amount of a solution is placed onthe substrate, which is then rotated at high speed to spread the fluidby centrifugal force. In addition to aqueous solutions, aqueoussuspensions and non-aqueous solvents can also be used for LbL assembly.

LbL assembly offers several advantages over other thin film depositionmethods. Without using instruments, LbL technique can prepare multilayerfilms by dipping a substrate sequentially into different solutions,which makes the technique simple. One important quality of LbL assemblyis the high degree of control over thickness due to the linear growth ofthe film thickness with the number of bilayers. Another advantage of LbLassembly is that many different materials can be incorporated inindividual multilayer films.

LbL can be used to deposit oppositely charged materials, such as apolyanion and a polycation. A polyanion has a plurality of negativelycharged functional groups, such as sulfonated polystyrene (SPS) orpoly(acrylic acid), or a salt thereof. Graphene oxide (GO) ishydrophilic and often contains carboxyl groups and other functionalgroups. When dispersed in aqueous solution, GO becomes negativelycharged in a solvent such as water. A polycationic polymer can be apolyamino acid, polyethylimine, polyallylamine, polylysine,polyornithine, polyethyleneimine, or mixtures or copolymers thereof.

LbL can also be used to deposit materials otherwise having affinity foreach other. For example, in addition to relying on the electrostaticattraction between molecules of opposite charges, hydrogen-bondinginteractions can also be used to produce multilayers. For instance,poly(carboxylic acid) and polymers containing electron-donatingfunctional groups can be assembled into multilayers. Poly(carboxylicacid) can include poly(acrylic acid) (PAA) or poly-(methacrylic acid)(PMAA). Materials containing electron-donating functional groups includepoly(ethylene oxide) (PEO), poly(vinyl alcohol), andpoly(vinylpyrrolidone). In addition, that neutral polymer PEO andanionic GO can form an LbL multilayer films also suggestsnonelectrostatic interactions can drive layer by layer assembly.

A bilayer LbL films can be formed by depositing alternating layers ofoppositely charged materials or materials otherwise having affinity foreach other. Optionally, a wash step can be used in between depositingsteps to remove excess material and improve layer quality. A multilayerfilm can be formed by repeating this process. For example, a tetralayerfilm can be made by depositing a total of four alternating layers, i.e,two layers of bilayers. A single tetralayer can form a protective layeron an electrode surface. Alternatively, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11,12, 13, 14, 15 or more tetralayers can be used.

FIG. 1 is a schematic drawing depicting a multilayer structure, apolymer tetralayer structure according to one embodiment. As shown inFIG. 1, 101 is a layer containing a first material, 102 is a layercontaining a second material, 103 is a layer containing a thirdmaterial, and 104 is a layer containing a fourth material. A firstmaterial in 101 and a third material in 103 can be the same ordifferent; a second material in 102 and a fourth material in 104 can bethe same or different. Adjacent layers can contain oppositely chargedmaterials. For example, 101 and 103 can be anionic layers, and 102 and104 can be cationic layers; alternatively, 101 and 103 can be cationiclayers, and 102 and 104 can be anionic layers. Otherwise, adjacentlayers in FIG. 1 represent materials having affinity for each other,such as hydrogen-bonding interactions.

The multilayer structure can be formed on a membrane, a substrate, or amembrane attached to a substrate. LbL assembly can use a variety ofsubstrates, including oxides (glass quartz, Si, TiO2, mica etc.), noblemetals (Au, Pt, etc.), and synthetic polymers (polyethyleneterephthalate (PET), poly(methyl methacrylate) (PMMA), polyetherimide,etc.). LbL assembly can also be performed on a polymer membrane attachedon a substrate, such as a polypropylene membrane attached on a glasssubstrate. The multilayer structure can include ion-conductive polymerand any of the layers can be a barrier layer.

Using LbL technique, multilayer films comprising one or more tetralayersof PEO/GO/PEO/PAA can be prepared. PEO can be used as an ion conductivepolymer. Other ion conductive polymers include polyethyleneimine,polyacrylonitrile, and polysaccharides. GO can serve as an electricalinsulator; in addition, being hydrophilic, GO disperses readily inwater. When a PEO/GO/PEO/PAA multilayer film is built up on anelectrode, it can function as protective layers. For example, aPEO/GO/PEO/PAA multilayer film can hinder short-circuit caused byLithium dendrite and improve charge-discharge cyclability of lithium-airbatteries. A GO layer can be a barrier layer.

The thickness of GO sheet before dispersing in water can be about 1 nm.PEO with a degree of polymerization more than 2000 (Mw=100,000 Da), andPAA with a degree of polymerization more than 600 (Mw=50,000 Da) can beused. GO is an extremely thin material and limited to pile up thickly byhydrogen bonding. This consequently yields thinner build-up of LbLmultilayers with GO than PEO/PAA pair without GO. In addition, thethickness of LbL assemblies grew linearly.

FIG. 2 is a schematic view showing a battery according to oneembodiment. As shown in FIG. 2, a battery can include a first electrode201, a second electrode 205, and an electrolyte 203. The battery canalso include a separator 204 (not shown) between a first electrode 201and a second electrode 205. The first electrode 201 can contact a firstcurrent collector 206 (not shown), and the second electrode 205 cancontact a second current collector 207 (not shown). A first electrode201 is coated with a protective layer (or protective layers) 202.Alternatively, a second electrode 205 can be coated with a protectivelayer (not shown). The protective layer 202 can be a multilayerstructure shown in FIG. 1, such as a PEO/GO/PEO/PAA multilayer film. APEO layer in 202 can be next to electrode 201.

One electrode (either first electrode 201 or second electrode 205) caninclude a metal, an alloy, or a carbon-based material, e.g., porouscarbon, graphite, a nanostructured conductive carbon, organic polymers,other carbon-based materials, carbon-supported metal oxides such asTiO₂, or combinations of these. A carbon-based electrode can optionallyinclude binders, additives, or other materials.

The battery in FIG. 2 can be a metal/carbon battery, e.g., where oneactive material is a metal such as lithium, sodium, magnesium, calcium,or zinc. The battery in FIG. 2 can be a lithium battery, i.e., where oneelectrode (either first electrode 201 or second electrode 205) includeslithium metal or a lithium compound, such as a lithium metal oxide(e.g., a lithium cobalt oxide or a lithium manganese oxide). The term“battery” as used herein includes primary and secondary (rechargeable)batteries. Examples of lithium batteries include but are not limited toLi batteries (i.e., lithium metal batteries), Li-ion batteries, Li-ionpolymer batteries, Li-air batteries, Li—MnO₂ batteries, Li—S batteries,Li—SOCl₂ batteries, Li—SOCl₂—BrCl batteries, Li—SO₂Cl₂ batteries, Li—SO₂batteries, Li—(CF)_(x) batteries, Li—I₂ batteries, Li—Ag₂CrO₄ batteries,Li-silver vanadium oxide (SVO) batteries; Li—CuO batteries, Li-copperoxyphosphate batteries, Li—CuS batteries, Li—PbCuS batteries, Li-ironbatteries, Li-lead bismuthate batteries, Li—Bi₂O₃ batteries, Li-titanatebatteries, Li—V₂O₅ batteries, Li—CoO₂ batteries, Li/Al—MnO₂ batteries,or Li/Al—V₂O₅ batteries. In particular, Li-ion, Li-ion polymer, andLi-air batteries can be useful as rechargeable batteries.

Currently, 34% of the world's total primary energy source comes from oilwhere prices are increasing due to declining fossil fuel reserves. Itproduces 40% of the total CO₂ emission, which is a major cause of globalwarming. Energy consumption and global climate change suggest lookingfor an alternative energy conversion/storage system. Electrification ofroad transportation and large-scale development of renewable energy areinevitable strategies to address these environmental issues. The majortechnical hurdle for this transformation is the insufficient storagecapacity of the current energy storage system.

Rechargeable Lithium-ion batteries have been considered as a hope owingto their high energy density and efficiency. However, the highest energystorage that Li-ion battery can generate is too low to be satisfactoryfor key markets such as electrical vehicles. On the other hand,Lithium-air batteries can provide extremely high energy storagecapability in comparison to other rechargeable batteries, and thus seemto be one promising alternative. Even though the estimated practicalenergy density of Li-air batteries is much lower (˜1700 Wh/kg) than thetheoretical value (12 kWh/kg), it is sufficient to drive electricalvehicles of more than 500 km per charge, which is comparable to gasolinevehicles.

Since the first Li-air battery reported in 1996, Li-air batteries haveshown promising electrochemical performance for practical applications.One of the unique features of Li-air batteries is their open cellstructure due to unusual active material, oxygen from ambient air, forcathode reaction. Oxygen is absorbed from the environment instead ofbeing stored in the battery. Another notable feature of Li-air batteriesis the use of lithium metal as an anode material that has the highestspecific capacity (3862 mAh/g). On discharge, the lithium metaloxidized, releasing Li⁺ ion into the electrolyte, and oxygen moleculeswhich diffuse into the battery reduced by catalyst in the carbon-basedair electrode to form Li—O₂ compound. The reaction mechanisms of Li-airbatteries differ according to the electrolyte, non-aqueous or aqueoussolvent, though all systems use Li metal and oxygen gas as an anode andcathode material. The theoretical voltage of Li—O₂ reaction in aqueouselectrolyte is high (E₀=3.43 V for alkaline electrolyte and E₀=4.26 Vfor acidic electrolyte), but decomposition of aqueous electrolyte,safety issue between Li and electrolyte, and large volume of stackedcells due to the thick ceramic membrane prohibit the realization ofaqueous type Li-air batteries. Therefore, the Li-air batteries usingnon-aqueous electrolyte are focused on. The non-aqueous Li-air batteriesalso face some challenges. These issues mainly include development ofelectrochemically stable electrolyte, highly efficient catalyst,optimized structure of air electrode, and suppression of dendriticgrowth on Li anode.

Li-anode protective layers can suppress Li dendritic growth on the anodesurface of the Li-air batteries and enhance the cyclability of batterycells. High ionic conductivity and Li-ion transfer number,physical/chemical homogeneity at the contact surface with Li anode,controlled electrolyte permeability and longer dendrite short-circuittime are crucially required properties for Li-anode protective layer.Usually, polymer separators that directly contact on Li-anode are placedbetween anode and air electrode during the cell assembly to preventshort circuits of devices and absorb liquid electrolyte. For bothanode-protection and separation between anode and cathode, a simple anduniversal way is developed to modify commercially available polymermembrane with ion-conductive polymer and graphene oxide (GO) viaLayer-by-Layer (LbL) assembly. Polyethylene oxide (PEO), Liion-conductive polymer, and polyacrylic acid (PAA) can be used toprepare LbL films. GO can be incorporated as an anionic material andbarrier layer to prevent chemical fluctuation on the surface ofLi-anode. Several cycles of (PEO/GO/PEO/PAA) tetralayer can be built upon the anode-facing side of membrane. LbL-modified membranes can showhigh ionic conductivity and Li transfer number, and low electrolytepermeability. Short-circuit caused by Li dendrite can be hindered andcharge-discharge cyclability of Li-air cells can be improved.

Examples Materials and Instruments:

PEO (Mw=100,000 Da), 1,2-dimethoxyethane (DME) and hydrochloric acid(HCl) were obtained from Sigma-Aldrich, Inc. PAA (Mw=50,000 Da) waspurchased from Polysciences, Inc. Lithium bis(oxalate)borate (LiBOB) andpolypropylene (“PP”) membrane (Celgard 2400) were provided by Chemetalland Celgard, LLC., respectively. Custom-made electrolyte (0.1 M LiClO₄in DME) for electrochemical analysis was obtained from Novolytetechnologies. Li foil was obtained from Alfa Aesar. Graphene oxide wassynthesized by modified Hummer's method and used after dialysis atdeionized water for 7 days. X-ray photoelectron spectroscopy (XPS) showsthat abundant oxygen functional groups were induced on graphene sheetsafter oxidation (See FIG. 3). The average size of single sheet was 1.1μm and thickness was ˜1 nm.

Scanning electron microscopy (SEM) images were captured using JEOL 6700Fat 5 keV and 30 A of Au—Pd was sputter-deposited on the samples prior toimaging to suppress charging. Cross-sectional image was taken fromsamples immersed in liquid nitrogen and cleaved. Surface morphology ofthe LbL films was obtained by atomic force microscopy (AFM) usingDigital Instruments Multimode™ in tapping mode. Water contact angle onLbL-modified protective membrane was measured with Rame-hart.Profilometer (Veeco Dektak 150) was used to record the thickness of LbLlayers five times at different locations. The thicknesses were averagedto yield one data point and the standard deviation of the measurementswas taken as the error.

Layer-by-Layer Assembly on PP Membrane:

Layer-by-Layer (LbL) film was constructed using a programmable CarlZeiss DS-50 slide stainer. PP membranes were attached on glass substrateby narrow double sided-tape on all edges of membrane and treatedO₂-plasma for 30 seconds. The support membranes were first immersed in aPEO aqueous solution for 15 minutes (“min”) and rinsed in rinsingsolution for 2 min, followed by one 1 min rinse. Then, the substrate wasexposed to GO aqueous solution (0.17 mg/ml) for 15 min and rinsed asbefore. PP membrane was dipped in PEO solution again as before, and thenimmersed in PAA aqueous solution, another anion solution, for 15 min,followed by the same rinse process with deionized water. 20 μM ofpolymers was dissolved in all polymer solutions and 10 mM of LiBOB wasincluded for all polymer and polymer rinse solutions. For LbL assembly,pH of all solutions was adjusted to 2.5 for hydrogen bonding betweenmaterials. The tetralayer (TL) procedure was repeated desired times suchas 4 TL, 6 TL, 12 TL and 24 TL.

The procedure for PEO/GO/PEO/PAA LbL assembly on polymer membrane isdescribed in FIG. 4(a). LbL assembly on PP membrane was achieved byimmersing O₂ plasma-treated polypropylene membrane in PEO solution andtwo kinds of anionic solutions (GO and PAA), alternatively. GO wasincorporated as a barrier layer for controlled delivery of electrolyteand suppression of Li dendrite. Before O₂ plasma-treatment, PP membranewas attached on a slide glass to deposit LbL layers on only one side ofPP membrane. The pH for all solutions was adjusted to 2.5 to accomplishhydrogen bonding between materials and 10 mM of Lithiumbis(oxalate)borate (LiBOB) was dissolved in all polymer solutions toincrease ion conductivity and uniformity of LbL layers. PEO/GO/PEO/PAAtetralayers were repeatedly deposited as many times as desired.

Surface Properties of LbL Films:

FIG. 4(b) shows the scanning electron microscope (SEM) image of pristinemembrane, which has irregular porous structure. After O₂plasma-treatment, pore size of membrane was increased due to thedegradation of PP by O₂ plasma, but it still preserve porous structurewith sub-micron pores (See FIG. 5(a)).

After LbL assembly, it was observed that polymer layers and GO wereuniformly assembled on pristine membrane as shown in FIGS. 4(c) and4(d). Polymer layers smoothly covered the underlayers without any openpores or delamination. GO was deposited like papers due to its sheetstructure. However, GO sheets were not easily discovered incross-sectional view of SEM (FIG. 4(e)), because GO is extremely thinmaterial that has 1 nm of thickness and limited to stack thickly byhydrogen bonding or charge-charge interaction.

Contact angle with water droplets was measured to investigate theinfluence of LbL assembly on surface properties of polymer membrane.FIGS. 5(b) and 5(c) show contact angle images of LbL modified face andbare PP face. Since LbL modification was conducted only one side ofmembrane, the membrane is j anus-faced. LbL deposition decreased thecontact angle to 51.0°, while pristine PP had 104.7° of water contactangle. This implies that the LbL-modified membrane is more hydrophiliccompared to the bare PP membrane, so that more conformal interfacebetween Li metal and membrane is accomplished. In addition, hydrophobicPP side can protect Li anode by repelling any atmospheric moistureduring battery operation. Interestingly, electrolyte solvent (1,2-dimethoxyethane, DME) was well wetted on both sides to facilitatehomogeneous distribution of Li ions over the entire contact area with Limetal.

FIG. 6(a) shows the thickness of LbL layers as a function of the numberof tetralayers. In this figure, two bilayers of PEO/P AA were counted asa tetralayer for LbL assembly without GO. LbL assembly including GOexhibited lower increase of thickness than LbL assembly without GO atthe same number of tetralayers. As mentioned above, GO is an extremelythin material and limited to pile up thickly by hydrogen bonding. Thisconsequently yields thinner build-up of LbL multilayers than PEO/PAApair. In addition, the thickness of both LbL assemblies grew linearlyfrom 4 tetralayers. Lower rate of thickness increase under 4 tetralayersseems attributable to the hydrophobic nature of PP membranes in spite ofO₂ plasma treatment.

In practice, it is observed that LbL layers under 3 tetralayers didn'tuniformly cover the whole membrane surface and had some open pores owingto unfavorable absorption of polyelectrolytes on hydrophobic PP surface.After complete coverage over 4 tetralayers, the LbL layers presentlinear thickness growth with increasing cycle. Note that examined LbLlayers showed thicker thicknesses than those without dissolution ofLiBOB in polymer solutions because changing of polymer chainconformation from stretched, rodlike molecules to three-dimensionalrandom coils (See FIG. 7(a)).

Electrolyte Permeability:

Electrolyte permeability was determined by using modified wet-cupmethod. The membrane separated a dual-chamber apparatus, which containedelectrolyte at one side and was exposed to air at the other side. Theweight loss of electrolyte was monitored by precision balance at roomtemperature. The permeability of electrolyte was obtained from thevolume change of electrolyte and thickness of membrane as

$p = \frac{\mu \; Q\; {\Delta\chi}}{A\; \Delta \; P}$

where p is the permeability of a medium (m²), μ is the dynamic viscosityof the fluid (Pa·s) (For DME, 4.70×10⁻⁴ Pa·s), Q is the volume flow rateof the phase (m³/s, density of DME is 0.867 g/m³, and Δχ is thethickness of the bed of the porous medium (m). A corresponds to thecross sectional area (3.14×10⁴ m²), and ΔP is the applied pressuredifference (Pa).

P_(LbL) was calculated from the following series resistance model for abilayer membrane with LbL layer coating one side of the PP membrane:

$\begin{matrix}{\frac{1}{p_{total}} = {\frac{X_{LbL}}{p_{LbL}} + \frac{X_{PPmembrane}}{p_{PPmembrane}}}} & (1)\end{matrix}$

where X_(i) corresponds to the thickness fraction of component i andP_(i) is permeability of component i. The permeability of the LbL layer,P_(LbL), can be calculated from the measured permeability of the totalmembrane and PP substrate and the thickness fraction of all components.

Electrolyte permeabilities were repressed with increase of LbL thickness(See FIG. 6(c)). It is obvious that GO layers in LbL assemblyeffectively control the permeability than mere polymer multilayers. 4.20μm-thick LBL-modified membrane with GO showed 2.70×10⁻¹³ m² ofpermeability, while 7.43 μm-thick LbL-modified membrane without GO had1.03×10⁻¹² m² of permeability. Interestingly, the permeability of themodified membrane with only 170 nm-thick LbL layers (1.64×10⁻¹² m²) was4 times lower than pristine membrane (6.48×10⁻¹² m²).

Based on equation (1), intrinsic permeability of LbL layers can becalculated using series resistance model for LbL-modified membranes withor without GO. As shown in FIG. 6(d), the intrinsic permeability of 170nm-thick LbL layers was 1.48×10⁻¹⁴ m², dropping over two orders ofmagnitude than pristine membrane. In addition, the presence of GO in LbLlayers lowered the permeability about one order of magnitude.

Electrochemical Analysis:

For electrochemical analysis, DME 0.1 M LiClO₄ was used as anelectrolyte. Before electrochemical analysis, all samples vacuum-driedand stored in Ar-filled glove box for at least 1 week. Ionicconductivity measurements were carried out by impedance spectroscopywith a Solartron SI1260 impedance analyzer by sweeping the frequencyfrom 1 MHz to 1 Hz at 10 mV of ac amplitude. Test membrane withelectrolyte placed between two stainless steel electrodes in Swagelokcell. For Li transfer number, dendrite growth and cycling behavior,two-electrode Li cells were assembled in Ar-filled glove box with testmembrane and liquid electrolyte. The area of the Li electrode was 0.97cm² (1.11 cm in diameter) and two stainless steel rod current collectorswere used at both ends of the Swagelok cells to connect the electrode toa galvanostat (Solartron 1470E Cell Test System).

Li transfer number was determined by the combination of de polarizationand ac impedance analysis. The change of current according to the timewas monitored at constant potential (10 mV) for 7 days and ac impedancespectra were measured before and after polarization. The transportnumber is given by the following equation:

$\begin{matrix}{T_{+} = \frac{I_{s}\left( {{\Delta \; V} - {I^{0}R_{1}^{0}}} \right)}{I_{0}\left( {{\Delta \; V} - {I_{S}R_{1}^{s}}} \right)}} & (2)\end{matrix}$

where I_(s) and I₀ are the steady-state and the initial currentdetermined by the de polarization, respectively; ΔV is the de potentialapplied across the cell (10 mV); R₁ ⁰ and R₁ ^(s) are the interfacialresistance measured by the ac impedance analyzer before and afterpolarization.

Constant-current charging of the cells was conducted at current densityof 0.2 mA/cm² to observe Li dendrite growth. The time evolution ofvoltage (chronopotentiogram) between two Li electrodes was recorded andthe short-circuit time (t_(sc)) was defined as the time when a rapiddrop of the cell voltage was observed. Charge-discharge cycling also wascarried out by passing a constant current density (0.2 mA/cm²) andreversing its polarity every 4 hours (“h”).

Ionic Conductivities of LbL-Modified Membrane:

As shown in FIG. 6(b), ionic conductivities of LbL-modified membranewere changed with thickness increase of LbL layers. DME with 0.1 MLiClO₄ was used as electrolyte. The ionic conductivity (0.29 mS/cm) ofthe membrane with 170 nm-thick tetralayers (4 tetralayers, totalthickness of the membrane: 25.17 μm) was greatly improved than that ofpristine membrane (0.13 mS/cm, thickness of pristine membrane: 25 μm).It means PEO/GO/PEO/PAA multilayer is highly conductive even though GOis incorporated as a barrier layer. It is thought that relatively bigsize of bis(oxalate)borate anion gaped between polymer chains so thatmake easily the transport of ions. FIG. 7(b) clearly shows the effect ofGO and LiBOB on ionic conductivities of LbL-modified membranes. Theincorporation of GO decreases the ionic conductivity of membranes, butthe dissolution of LiBOB in polymer solutions promotes it at allthickness range to compensate the blocking effect of GO. However, ionicconductivities went down with increase of thickness by difficulty oftraversing thick films.

Li Transfer Numbers of LbL-Modified Membrane:

Li transfer number was explored to understand the true transportproperty of Li ions in LbL-modified membranes. It is determined by thecombination of de polarization and ac impedance. As shown in FIG. 8(a),when a small and constant potential is applied to the cell sandwiching amembrane and electrolyte between two Li electrodes, initial currentdecreases until steady-state value is reached. The anion current isdisappeared by concentration gradient across the cell in steady-statecurrent. Li transfer number is given by dividing steady-state current bythe initial current. LbL modified membrane with GO got the highersteady-state current than the membrane with mere polymer LbL layers,while they had almost the same initial current. However, duringpolarization, passivation layer also grows on the electrodes to inflictan increase of interfacial resistance.

FIG. 8(b) presents the change of interfacial resistance before and afterpolarization. The ac impedance spectra of the GO-incorporated membraneintersected higher Z′ that means larger bulk resistance than that of themembrane without GO before applying potential across the cell. Themembrane having LbL layers with GO, however, exhibited smallerinterfacial resistance than the membrane without GO. The difference ofinterfacial resistance became much bigger after polarization. Thediameter of hemisphere for the membrane without incorporation of GO grew4 times than before, while twofold increase of hemisphere size wasobserved in the cell using the LbL-modified membrane with GO. Litransfer number can be corrected by subtracting additional voltage dropby passivating layers from the applied potential (equation (2)).

FIG. 8(c) compares the Li transfer numbers of LbL-modified membranes andpristine membrane. LbL-assembled membrane with GO shows a little bitsmaller T₊ than pristine membrane (0.59) and their T₊ decrease withincrease of LbL thickness. But, the values are much higher than T₊ ofLbL-modified membrane without GO. The T₊ of membrane with GO was 0.52,while the membrane without GO had 0.21 at the same thickness of LbLlayers (470 nm). GO is helpful for Li ion transport through themembrane.

Dendrite Growth of LbL-Modified Membrane:

Dendrite growth on Li anode surface and cyclability are also examined.While 0.2 mA/cm² of current density was applied on two Li electrodecells, voltage change was monitored as a function of time. Forcyclability test, the polarity of current density is reversed every 4 h.As shown in FIG. 9(a), sudden voltage drop means short circuit due tothe dendrite growth on Li anode and punching out the membrane. Whilepristine membrane endured just 11 h, LbL-modified membrane with 6tetralayers stood 281.8 h. FIG. 11 is a table that shows theshort-circuit time of two Li electrode cell with pristine andLbL-modified membrane with GO or without GO. LbL modification ofpristine membrane with GO effectively suppressed the dendritic growth onLi anode. That is also found in cycling test. As shown FIG. 9(b) andFIG. 10, LbL modified membrane with GO stood over 40 cycles, whileLbL-modified membrane without GO stood only 6 cycles and pristinemembrane endured 25 cycles.

Other embodiments are within the scope of the following claims.

What is claimed is:
 1. A multi-layer structure comprising a tetralayer,wherein the tetralayer includes an ion-conductive polymer and a barrierlayer.
 2. The structure of claim 1, wherein the tetralayer is on asubstrate.
 3. The structure of claim 2, wherein the substrate includes apolymer membrane.
 4. The structure of claim 3, wherein the polymermembrane includes polypropylene.
 5. The structure of claim 1, whereinthe tetralayer includes graphene oxide, polyethylene oxide orpolyacrylic acid.
 6. The structure of claim 1, wherein the tetralayerincludes a first polyethylene oxide layer, a graphene oxide layeradjacent to the first polyethylene oxide layer, a second polyethyleneoxide layer adjacent to the graphene oxide layer and opposite the firstpolyethylene oxide layer, and a polyacrylic acid layer adjacent to thesecond polyethylene oxide layer.
 7. The structure of claim 6, whereinthe tetralayer is on a polypropylene membrane.
 8. The structure of claim2, wherein the surface of the tetralayer is more hydrophilic than asurface of the substrate.
 9. The structure of claim 1, wherein thethickness of the structure increases as the number of tetralayersincreases.
 10. The structure of claim 1, wherein increasing thethickness of the tetralayer changes the ionic conductivities of thestructure.
 11. The structure of claim 1, wherein electrolytepermeability are repressed with increasing thickness of the tetralayer.12. The structure of claim 1, wherein graphene oxide lowers thepermeability.
 13. A battery device comprising an electrode protectivestructure, wherein the electrode protective structure includes grapheneoxide.
 14. The device of claim 13, wherein the battery is a lithiumbattery or a lithium-air battery.
 15. The device of claim 13, whereinthe electrode protective structure contacts a surface of an anode. 16.The device of claim 13, wherein the electrode protective structureincludes ion-conductive polymer, a barrier layer, polyethylene oxide, orpolyacrylic acid.
 17. The device of claim 13, wherein the electrodeprotective structure includes a first polyethylene oxide layer, agraphene oxide layer adjacent to the first polyethylene oxide layer, asecond polyethylene oxide layer adjacent to the graphene oxide layer andopposite the first polyethylene oxide layer, and a polyacrylic acidlayer adjacent to the second polyethylene oxide layer.
 18. The device ofclaim 17, wherein the electrode protective layers are formed on apolypropylene membrane.
 19. The device of claim 17, wherein theelectrode protective layers suppress dendritic growth on an electrode.20. The device of claim 17, wherein the electrode protective layerssuppress dendritic growth on a lithium anode.